The present invention relates to an aqueous suspension formulation of encapsulated pesticide.
Recently, aqueous suspension of encapsulated pesticide which is obtainable by microencapsulation process of a pesticidal active ingredient in water have been attracted attention in view of stabilization of active ingredient, persistency of efficacy, decrease of toxicity and so on.
It is known to add a thickner, such as polysalcharides and mineral powders, for keeping an aqueous suspension of encapsulated pesticide stable for a long period. However, the excess addition of a thickner makes the aqueous suspension sticky and it often causes the difficulty of dealing the aqueous suspension.
The object of the present invention is to serve an aqueous suspension formulation of encapsulated pesticide which is easy to handle and excellent in preservative stability.
The present invention is the aqueous suspension formulation of encapsulated pesticide containing a specific amount of a specific nonionic water-soluble substance.
In other words, the present invention relates to an aqueous suspension formulation of encapsulated pesticide comprising 3 to 30% by weight of nonionic water-soluble substance which is solid at room temperature and has 50 to 700 of molecular weight (hereinafter referred as xe2x80x9cthe present microencapsulated slurry formulationxe2x80x9d). The present microencapsulated slurry formulation is also highly antiseptic.
The water-soluble substance utilized in the present invention has 50 to 700 of molecular weight, and it is solid at room temperature and nonionic water-soluble substance. And it usually has no surfactant ability. Examples of the water-soluble substance used in the present invention include water-soluble organic compounds such as sugars (e.g. monosaccharide oligosaccharide and so on) and urea (molecular weight:60).
Examples of the monosaccharide include triose such as glyceraldehyde (m.w.:90) and dioxyacetone (m.w.:90); tetraose such as erythrose (m.w.:120), threose (m.w.:120) and erythrulose (m.w.:120); pentose such as ribose (m.w. :150), arabinose (m.w.:150), xylose (m.w.:150), lyxose (m.w.:150) and xylulose (m.w.:150); hexose such as glucose (m.w.:180), mannose (m.w.:180), galactose (m.w.:180), fructose (m.w.:180), sorbose (m.w.:180) and tagatose (m.w.:180); heptose such as mannoheptose (m.w.:210) and sedoheptulose (m.w.:210); and monosaccharide derivatives such as sorbitol (m.w.:182), mannitol (m.w.:182) and glucuronic acid (m.w.:194).
Examples of the oligosaccharide include disaccharide such as cellobiose (m.w.:342), trehalose (m.w.:342), lactose (m.w.:342) and sucrose (m.w.:342); trisaccharide such as maltotriose (m.w.:504); and tetrasaccharide such as maltotetraose (m.w.:666). The amount of the water-soluble substance used in the invention is 3 to 30% by weight, preferably 5 to 20% by weight in the present microencapsulated slurry formulation.
The present microencapsulated slurry formulation is an aqueoue suspension of microcapsules (microencapsulated pesticidal active ingredient in the wall substance) and usually comprises an encapsulated pesticidal active ingredient, the water-soluble substance used in the invention, water, a disersant and optionally additives such as a preventing agent for precipitating crystaline, a fluidity-adjusting agent and an antifreezing agent.
The average diameter of the microcapsules is usually 0.1 to 200 xcexcm, preferably 1 to 100 xcexcm.
The pesticidal active ingredients include insecticidal, fungicidal, herbicidal, plant growth regulating and insect growth regulating compounds and so on, and are exemplified by organophosphorus compounds such as fenitrothion[O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate], fenthion[O,O-dimethyl O-(3-methyl-4-(methylthio)phenyl)phosphorothioate], diazinon[O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos[O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate[O,S-dimethyl acetylphosphoramidothioate], methidathion[S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-dimethyl phosphorodithioate], disulfoton[O,O-diethyl S-2-ethylthioethyl phosphorodithioate], DDVP[2,2-dichlorovinyl dimethyl phosphate], sulprofos[O-ethyl O-4-(methylthio)phenyl S-propyl phosphorodithioate], cyanophos[O-4-cyanophenyl O,O-dimethyl phosphorothioate], dioxabenzofos[2-methoxy-4H-1,3,2-benzodioxaphosphorine 2-sulfide], dimethoate[O,O-dimethyl S-(N-methylcarbamoylmethyl) dithiophosphate], phenthoate[ethyl 2-dimethoxyphosphinothioylthio(phenyl)acetate], malathion[diethyl (dimethoxyphosphinothioylthio)succinate], trichlorfon[dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azinphos-methyl[S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O,O-dimethyl phosphorodithioate], monocrotophos[dimethyl {(E)-1-methyl-2-(methylcarbamoyl)vinyl}phosphate], ethion[O,O,Oxe2x80x2,Oxe2x80x2-tetraethyl-S,Sxe2x80x2-methylenebis(phosphorodithioate)] and so on; carbamate compounds such as BPMC [2-sec-butylphenyl methylcarbamate], benfuracarb[ethyl N-{2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio}-N-isopropyl-xcex2-alaninate], propoxur[2-isopropoxyphenyl N-methylcarbamate], carbosulfan[2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl N-dibutylamninothio-N-methylcarbamate], carbaryl[1-naphthyl N-methylcarbamate], methomyl[S-methyl N-(methylcarbamoyloxy) thioacetimidate], ethiofencarb[2-(ethylthiomethyl)phenyl methylcarbamate], aldicarb [2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime], oxamyl[N,N-dimnethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide], fenothiocarb[S-4-phenoxybutyl N,N-dimethylthiocarbamate], and so on; pyrethroid compounds such as etofenprox[2-(4-ethoxyphenyl)-2-methyl-1-(3-phenoxybenzyl)oxypropane], fenvalerate[(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate], esfenvalerate[(S)-xcex1-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin[(RS)-xcex1-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin[(RS)-xcex1-cyano-3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], permethrin[3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], cyhalothrin[(RS)-xcex1-cyano-3-phenoxybenzyl (1RS,3Z)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], deltamethrin[(S)-xcex1-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate], cycloprothrin[(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate[xcex1-cyano-3-phenoxybenzyl N-(2-chloro-xcex1, xcex1, xcex1-trifluoro-p-tolyl)-D-valinate], bifenthrin[2-methyl-3-phenylbenzyl (1RS,3Z)-cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate], halfenprox[2-(4-bromodifluoromethoxyphenyl)-2-methyl-1-(3-phenoxybenzyl) methylpropane], tralomethrin[(S)-xcex1-cyano-3-phenoxybenzyl (1R)-cis-3-(1,2,2,2-tetrabromoethyl)-2,2-dimethylcyclopropanecarboxylate], silafluofen[(4-ethoxyphenyl)-{3-(4-fluoro-3-phenoxyphenyl)propyl}dimethylsilane], d-phenothrin[3-phenoxybenzyl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], cyphenothrin[(RS)-xcex1-cyano-3-phenoxybenzyl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], d-resmethrin[5-benzyl-3-furylmethyl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], acrinathrin[(S)-xcex1-cyano-3-phenoxybenzyl (1R,3Z)-cis-(2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl}cyclopropanecarboxylate], cyfluthrin [(RS)-xcex1-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], tefluthrin[2,3,5,6-tetrafluoro-4-methylbenzyl (1RS,3Z)-cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate], transfluthrin[2,3,5,6-tetrafluorobenzyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], tetramethrin[3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate], allethrin[(RS)-2-methyl-4-oxo-3-(2-propenyl)-2-cyclopenten-1-yl (1RS)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate], prallethrin[(S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopenten-1-yl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate], empenthrin[(RS)-1-ethynyl-2-methyl-2-pentenyl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], imiprothrin [2,5-dioxo-3-(2-propynyl)imidazolidin-1-ylmethyl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], d-furamethrin[5-(2-propynyl)furfuryl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], 5-(2-propynyl)furfuryl2,2,3,3-teramethylcyclopropanecarboxylate and so on; thiadiazine derivatives such as buprofezin[2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one] and so on; nitroimidazolidine derivatives such as imidacloprid[1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and so on; nereistoxin derivatives such as cartap[S,Sxe2x80x2-(2-dimethylaminotrimethylene)bis(thiocarbamate)], thiocyclam[N,N-dimethyl-1,2,3-trithian-5-ylamine], bensultap[S,Sxe2x80x2-2-dimethylaminotrimethylenedi(benzenethiosulfonate)] and so on; N-cyanoamidine derivatives such as N-cyano-Nxe2x80x2-methyl-Nxe2x80x2-(6-chloro-3-pyridylmethyl)acetamidine and so on; chlorinated hydrocarbon compounds such as endosulfan[6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], xcex3-BHC[1,2,3,4,5,6-hexachlorocyclohexane], dicofol[1,1-bis(4-chlorophenyl)-2,2,2-trichloroethanol]; benzoylurea compounds such as chlorfluazuron[1-{3,5-dichloro-4-(3-chloro-5-trifluromethylpyridin-2-yloxy)phenyl}-3-(2,6-difluorobenzoyl)urea], teflubenzuron[1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea], flufenoxuron[1-{4-(2-chloro-4-trifluromethylphenoxy)-2-fluorophenyl}-3-(2,6-difluorobenzoyl)urea] and so on; formarnidine derivatives such as amitraz[N,Nxe2x80x2-{(methylimino)dimethylidine}-di-2,4-xylidine], chlordimeform[Nxe2x80x2-(4-chloro-2-methylphenyl)-N,N-dimethylmethinimidamide] and so on; thiourea derivatives such as diafenthiuron[N-(2,6-diisopropyl-4-phenoxyphenyl)-Nxe2x80x2-t-butylcarbodiimide] and so on; N-phenylpyrazole compounds; metoxadiazone[5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2-(3H)-one]; bromopropylate[isopropyl4,4xe2x80x2-dibromobenzilate]; tetradifon[4-chlorophenyl2,4,5-trichlorophenyl sulfone]; chinomethionat[S,S-6-methylquinoxaline-2,3-diyl dithiocarbonate]; propargite[2-(4-tert-butylphenoxy)cyclohexylprop-2-yl sulfite]; fenbutatin oxide[bis{tris(2-methyl-2-phenylpropyl)tin}oxide]; hexythiazox[(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide]; clofentezine[3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine]; pyridaben[2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one]; fenpyroximate[tert-butyl(E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate]; tebufenpyrad[N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide]; polynactin complex[tetranactin, dinactin, trinactin]; pyrimidifen[5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidin-4-amine]; milbemectin; abamectin; avermectin; azadirachtin[AZAD]; 5-methyl[1,2,4]triazolo[3,4-b]benzothiazole; methyl1-(butylcarbamoyl)benzimidazole-2-carbamate, 6-(3,5-dichloro-4-methylphenyl)-3(2H)-pyridazine; 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butanone; (E)-4-chloro-2-(trifluoromethyl)-N-[1-(imidazol-1-yl)-2-propoxyethylidene]aniline; 1-[N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]carbamoyl]imidazole; (E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)-1-penten-3-ol; 1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol; (E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)-1-penten-3-ol; 1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol; 4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorphorine; 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol; O,O-diethyl O-2-quinoxalinyl phosphorothioate; O-(6-ethoxy-2-ethyl-4-pyrimidinyl) O,O-dimethyl phosphorothioate; 2-diethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate; 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl p-toluenesulfonate; 4-amino-6-(1,1-dimethyethyl)-3-methylthio-1,2,4-triazin-5(4H)-one; 2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide; 2-methoxycarbonyl-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide; 2-methoxyearbonyl-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide; 2-methoxycarbonyl-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide; 2-ethoxycarbonyl-N-[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]benzenesulfonamide; 2-(2-chloroethoxy)-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide; 2-methoxycarbonyl-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]phenylmethanesulfonamide; 2-methoxycarbonyl-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]thiophene-3-sulfonamide; 4-ethoxycarbonyl-N-[(4,6-dimnethoxypyrimidin-2-yl)aminocarbonyl]-1-methylpyrazole-5-sulfonamide; 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolinecarboxylic acid; 2-[4,5-dihydro-4-methyl4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylic acid; methyl -6-(4-isopropyl-4-methyl-5-oxoimidazolin-2-yl)-m-toluate; methyl2-(4-isopropyl-4-methyl-5-oxoimidazolin-2-yl)-p-toluate; 2-(4-isopropyl-4-methyl-5-oxoimidazolin-2-yl)nicotinic acid; and N-(4-chlorophenyl)methyl-N-cyclopentyl-Nxe2x80x2-phenylurea.
The content of the pesticidal active ingredient in the present microencapsulated slurry formulation is usually 1 to 50% by weight, preferably 5 to 35% by weight. And the content of the wall substance to form the rnicrocapsules is usually 0.01 to 15% by weight, preferably 0.1 to 5% by weight based on the weight of the present microencapsulated slurry formulation. Further, the content of water is usually 30 to 90% by weight based on the weight of the present microencapsulated slurry formulation.
Examples of the microencapsulation method include interfacial polymerization method wherein microcapsule is prepared by allowing monomers, dissolved in two solvents which cannot be mixed each other, to react at the interface of the solvents (interfacial polymerization reaction) for affording polymer; in-situ method wherein microcapsule is prepared by allowing monomer, dissolved in one of two solvents which cannot be mixed each other, to react at the interface of the solvents for forming uniform wall on the surface of the core substance; phase separation method (coacervation method) that is utilized a phenomenon (coacervation) separating a thicker phase with a thinner phase by a slight change of solvent components of polymer solution wherein microcapsule wall is prepared by separating one or more colloidal polymer out at the interface by addition of a phase-separation inducing agent that has a high affinity with solvent, joint electrostatic action or hydrogen bonding; and solvent evaporation method wherein core liquid or core solid is dispersed in a solvent dissolving polymer that can form a wall material, the dispersion is further dispersed in a solvent that cannot be mixed with the above solvent, and then the above solvent is gradually evaporated to deposit polymer at the interface of the core substance.
Examples of the wall substance to form microcapsules include polyurea, polyurethane, polyamide, urea-formalin resin, melamin-formalin resin, gelatin, albumin and chitosan.
The above microencapsulation methods and the sort of the wall substances are suitably set for the objects.
The average wall thickness of the microcapsules is usually 0.001 to 10 xcexcm, preferably 0.01 to 5 xcexcm.
The method for adding the water-soluble substance used in the invention is not limited. It may be added to slurry of the microencapsulated pesticidal active ingredient or it may be added prior to microencapsulation. But it is preferable to add the water-soluble substance used in the invention to the slurry of the microencapsulated pesticidal active ingredient.
Examples of the dispersant include natural polysaccharides such as gum arabic; water-soluble polymer such as polyvinyl alcohol; and surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants and zwitter-ionic surfactants. The content of the dispersant in the formulation of the present invention is usually 0.1 to 10% by weight, preferably 1 to 5% by weight. The dispersant is usually added prior to microencapsulation.
Examples of the preventing agent for precipitating crystalline include aromatic hydrocarbons such as phenyixylylethane, methylnaphthalene and alkylbenzene; aliphatic hydrocarbons such as hexane, octane and decane; ketones such as isophorone and cyclohexanone; esters such as dialkyl adipate (e.g. diisodecyl adipate, diisobutyl adipate) and dialkyl phthalate (e.g. ditridecyl phthalate); and N-alkylpyrrolidone such as N-methylpyrrolidone. The content of the preventing agent for precipitating crystalline is usually 1 to 40% by weight , preferably 10 to 30% by weight. The preventing agent for precipitating crystalline is usually added prior to microencapsulation.
Examples of the fluidity-adjusting agents include natural polysaccharides such as xanthan gum, rhamsan gum, locustbean gum, carageenan and welan gum; synthetic polymers such as sodium polyacrylate; semi-synthetic polymers such as carboxymethylcellulose; mineral powders such as alminium silicate, smectite, bentonite, heclite and dry process silica; alumina sol; and so on. The content of the fluidity-adjusting agents is usually 0.01 to 5% by weight , preferably 0.05 to 1% by weight. The fluidity-adjusting agents is usually added to slurry of the microencapsulated pesticidal active ingredient.
The formulation of the present invention may optionally comprises the other auxiliaries for formulation. Examples of the auxiliaries include antifreezing agents. The typical example of the antifreezing agents is alcohols such as propylene glycol.
The present microencapsulated slurry formulation can be applied by usual method depending on the pesticidal active ingredient in the same situation that ordinary aqueous microsuspension formulation is applied. For example, it may be applied by itself or as a water dilution for pest-controlling in paddy or field, weed-controlling in paddy or field, termite-controlling in house and cockroach-controlling indoors. As the formulation of the present invention has a low viscosity, the formulation is easily taken out a container. Therefore, it is especially useful in case that it is desired to apply a large amount of pesticide in a short tine, such as aerial application use, termite-controlling use in house and cockroach-controlling use indoors.
When it is utilized in aerial application, 0.8 to 40 liters of the present microencapsulated slurry formulation or its dilution can be usually applied per 1 hectare. One to 5 liters is standardly applied for soil-treatment of termite-controlling in house, 50 to 400 mrliliters is standardly applied for wood-treatment of termite-controlling in house and 10 to 100 mililiters is standardly applied for cockroach-controlling indoors per 1 m2. The concentracion of the formulation of the present invention can be suitably set according to the desired dosage of the utilized pesticidal active ingredient.